Abstract
Atomically thin two-dimensional alloys are interesting for electrocatalysis but suffer from poor functional robustness and wide active-site heterogeneity. Here the synthesis of an unconventional hexagonal close-packed-phase intermetallic Pd-based multi-metallene, on which isolated Ru–O3 atomic sites are homogeneously dispersed, overcomes these obstacles. This structure exhibits excellent hydrogen oxidation reaction (HOR) activity, durability and anti-CO poisoning performance. The mass activity and exchange current density reach 11.5 mA μg−1 and 1.0 mA cm−2, respectively, showing some of the fastest reaction kinetics reported for Pd-based HOR catalysts. In situ Raman spectroscopy and theoretical investigations confirm that the intensified ligand effect derived from orderly atomic arrangement tends to strengthen the adsorption of hydroxyl and water, while the homogeneous Ru–O3 sites contribute to weakened binding of HOR-involved intermediates (*H, *OH and *H2O), leading to a favourable reaction pathway. This work demonstrates the importance of high-valence Ru and surface O species in enhancing the synergetic process and water reorganization.
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Acknowledgements
This study was financially supported by the National Science Fund for Distinguished Young Scholars (No. 52025133), the National Key R&D Program of China (No. 2022YFE0128500), the National Natural Science Foundation of China (Nos. 52261135633 & 22479002), the Beijing Outstanding Young Scientist Program, the China National Petroleum Corporation–Peking University Strategic Cooperation Project of Fundamental Research, the Beijing Natural Science Foundation (No. Z220020), the Tencent Foundation through the XPLORER PRIZE and the CNPC Innovation Fund (2021DQ02-1002). We thank the BL11B and BL14W1 photoemission photoendstations at the Shanghai Synchrotron Radiation Facility (SSRF) and the 1W1B beamline at the Beijing Synchrotron Radiation Facility (BSRF) for help with XAFS characterizations. We also acknowledge Y. Wei from M. Luo’s group at Peking University for microscopy operations, X. Liu from D. Su’s group at the Institute of Physics CAS for assistance with phase analysis and P. Zhou from Peking University Shenzhen Graduate School for DFT modelling advice.
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S.G. conceived and supervised the project. M. Luo and F. Lv guided and supervised the whole research. F. Lin and H.L. conducted all the experiments and jointly analysed the data. L.L. carried out the DFT calculations. Y.C. and Q.W. helped with XRD simulation. X.H., Y.L., X.Z., Q.Z. and L.G. contributed to aberration-corrected TEM characterization. D.W. and M. Li participated in part of the basic experiments. K.W. assisted with the electrochemical tests. F. Lin wrote the manuscript. All authors took part in the discussion of data and gave comments on the manuscript.
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Nature Synthesis thanks Carsten Streb, Huabing Tao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.
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Lin, F., Luo, H., Li, L. et al. Synthesis of isolated Ru–O3 sites on hexagonal close-packed intermetallic penta-metallene for hydrogen oxidation electrocatalysis. Nat. Synth 4, 399–409 (2025). https://doi.org/10.1038/s44160-024-00685-4
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DOI: https://doi.org/10.1038/s44160-024-00685-4
